Refining wax



Jan. 31, 1939. A. P. ANDERSON Er AL v`REFINING WAX A Filed larch4, 1936 Alvin p, Andelrson hama Jan. 31, 1939 TEATENTV OFFICE :44am ammo lwax lam. r. Anda-nn, man, ma Emma :.vnnn,

Wood River-,'Ill., signora to Shell Development Company, San poration offDelawara Francisco, Calif., a oor- Application Milch 4, 1936, Serial No, 87,118 10 (Cl. 196-18) Ihis invention relates yto the preparation of ymarketable paraffin wax from raw bulk wax and s milar wax mixtures, and is particularly concerned withsan improved method for separating hard waxes of light color from dark colored wax mixtures, which mixtures, may often contain hyf drocarbons which are liquid at ordinary temperatures.

',Parailin wax is most commonly obtained from` petroleum oils, particularly from reduced crudes ror wax distillates, by freezing them and separating the solidiiled wax kfrom the liquid 'components by Asome physical method, such as filtration or centrifuging. `In some instances, the separation of the wax is eifected in thev presence 'of a hydrocarbon diluent, such as propane, or

- @naphtha, or in the presence of a diluent exercis- Q to f orm nuclei for the wax.

Waxes obtained by any of theseA or other simiing selective solvent properties between the wax vvand the oil, such as a mixture of benzene and acetone. In certainother processes, the'oil is 'treated with a mineral acid, such asL sulfuric acid, under conditions causing the formation of pepper sludge, and the wax is solidiiied while the pepper sludge is maintained in suspension.

y lar methods are herein referred to as raw bulk waxes. They are solid or semi-solid at normal temperatures (from 40 F. to 90 F.) and, generally contain a considerable quantity of darkcolored material, and contain a variety of hyr drocarbons having diiferent melting points.

Since, as a general rule, the melting point of a mixture of substances is below the arithmetic mean of the ,melting points of the components of the mixture, it follows that such bulk waxes contain individual waxes having melting points which are considerably higher than the melting point' of the bulk wax.

For many purposes water white or very light i coloredy waxes are required; moreover, only the high-melting waxes are well suited for many particular applications, and these hard waxes are more valuable than the low-melting waxes. There are several methods known to the art for accomplishing the decolorization and isolation of individual waxes. Decolorization has heretoby clay treatment. For the separation of the components of the bulk wax, sweating, fractional distillation, extraction, etc., have been proposed.

Among the known processes for the separation of waxes, distillation is unsuited for the production of light colored, hard waxes, because after distillation, the bottoms, containing the hard waxes, still contain oil, and their melting points are, therefore, relatively low. Moreover, the coloring matter is concentrated in the bottoms and a severe treatment is required to produce a satisfactory light colored product, in addition to the sweating treatment, which is necessary to raise the melting point of the wax.

Sweating, withoutpreliminary distillation,

`could be employed for treating bulk waxes which already have good colors, the softer waxes being successively removed.y This process is, however, dimcult to handle, and the yield and melting point of hard waxes are low.

In attempting to produce light-colored, hard waxes from dark colored bulk waxes, such as black Mid-Continent bulk wax, we found it to be impractical to employ an acid treatment followed by sweating, because upon vbeing treated with acid, the raw waxes form oil-solubleacidic compounds, and these compounds make the usual finishing treatments uneconomical because of large amounts of clay required to obtain lightcolored products.

It .is an object of the present invention to provide an improved process for producing light colored, hard waxes in a combination of steps which improves the yield of hard waxes.

Briefly, our process consists in treating a norpropane, petroleum naphtha, or any other similar diluent, to form an acid sludge, separating the sludge' by settling, centrifuging, or any other physical method, and chilling the sour wax, preferably at a rate to insurelthe formation of illterable crystals, by indirect cooling or by partial evaporation of the diluent present in solution at a low pressure, and separatingfthe solidiiled wax from the liquid wax-diluent solution by any method, su'ch as iiltratioii. The chilling is stopped at one or more stages, and theindividual wax fractions, crystallized in the stepwise chilling, are collected separately. The sepa.- rated wax fractions may, if desired, be further finished with a clay treatment. The quantity of the diluent depends upon the viscosity of the Wax. In most cases, between 100% and 800% of diluent are suitable. The amount of acid used depends upon the wax being treated. For most purposes between 10 and 30% by volume of any strong concentrated mineral acid, such as between 90% and 100% H2804 is suitable. although our process is not restricted to these limits.

It was found that by fractionally precipitating the wax in this manner the fractionation efllciency was Agreatly increased, and that the melting points of the fractions, as well' as their yields, were increased, as compared with the former methods involving sweating, or fractional precipitation from a neutral medium. The wax should preferably have an acid content of above 0.2, expressed in mg. KOH per g. l

We have, further, found that the yield of hard wax can be greatly improved by adding a nely subdivided material, such as pulverized clay, to the liquid preferably acid, diluted wax before chilling, and the mixture is agitated to maintain the pulverized material in suspension during the chilling. 'I'he nne particles probably form nuclei for the crystallization of the higher-melting wax, and enhance the fractionation emciency of the process. This material may be added to the ltrate from each ltratiomstage, before the suc-A ceeding chilling step. This feature is particularly useful when combined with the above described method of fractionating acid-treated wax, the pulverized material being added to the wax after the removal of the acid sludge. While we prefer to employ about 2% by weight of pulverized, activated clay, other materials, such as activated silica, bentonite, etc., may be employed. The quantity'may also be varied Within wide limits, although we prefer to employ between .5 and 5%.

The pulverized material may be conveniently maintained in suspension by bubbling small amounts of gaseous propane through the solution during the chilling period. The rst filtration is made at a temperature depending upon the yield and melting point desired. The fraction obtained may be passed into a heating tank supplied with a mechanical stirring device, where the clay-wax propane fraction is heated and stirred to remove .propane and to contact the wax with the clay present in the fraction. The nished product is obtained after removal of the'clay by filtration. The contacting may be effected in a separate vessel, and in a separate operation. A processing step and heat may, however, be saved by filtering the molten wax directly after the vaporization of the solvent, such as propane, or after further heating in the same vessel.

Our invention may be further illustrated by the following examples, which are, however, given merely by way of elucidation, and not with a view of limiting the scope of the present invention:

Eauzmplel I A hard, black Mid-Continent bottom wax having a melting point of 134 F. obtained from the raw bulk wax upon removing 40% by vacuum distillation was mixed with 400% by volume lof liquid propane and 15% by weight of 93% sulfuric acid;

the mixture was heated to 140145 F. and well mixed to dissolve the wax, and the heated mixture was allowed to stand to eiect separation of the acid sludge.

One portion of the desludged Wax was neutra.- lized with 30 B. caustic soda solution and washed, and another portion was left unneutralized. These portions were separately chilled by evaporating a, portion of the propane, and filtered at the following temperatures: 80 F., '70 F., 60 F., and 30 F. The wax fractions obtained were then warmed and contacted with 10% of activated clay (Filtrol). The results were as follows:

(a) Undeterminable due to soep.

, The above results indicate that the precipitation of wax from an acid wax solution is far more advantageous than the precipitation from a neutralized wax solution containing oil-soluble soaps.

Example II In order to determine whether or not the soapy matter obtained in the neutralization was the cause of the faulty wax crystallization obtained in the above example, another portion of the acid treated and desludged wax was neutralized, the propane removed, and the treated wax was clay treated to remove the soap. The resulting wax was then again dissolved in liquid propane, and fractionated by step-wise chilling, and filtration at the following temperatures: 80 F., 60 F., and 40 F., and the wax fractions were contacted with 10% of activated clay. 'I'he results are shown in the following table:

Table II Percent by ASTM weight melting yield point Filtered at F.

80 F 18. 6 3+ 144 18. 2 D35+ 133 10.8 D34 129 By comparing the above results with those given in Table I, it will be noted that the absence of the soapy matter results in relatively larger yields; but the fractionation eiilciency is low, as is apparent from the lower` melting point of the precipitated wax.

vEmmple III Sour acid treated and desludged wax, as described in Example I, was chilled in several stages in the presence of 2% yoi' activated pulverized g5 I'lotshowthe applicability `of ,o our invention to clay added before each The `wax'.'fractions were'warmed to cause eilective oonteotwitn'the oiay contained in thetwox, .no

further yquantities` or clay iieiuirgddid..

The results were as follows z.

roble m Percent by ASTM f weight melting yield point 17kvv 13. 5 5+ ll f 6.0 3+ 1M 5. 5 3+ k 14a f 34.0 M+ 12s ,"It'` win be noted that the addition of the oulver'- 'f clay has amarked eilect upon the fractionationfenlcle'ncy, andresulted in a decided lm'- provement ofthe melting points of the irst three waxiractions f Y Y, L ExampleJV raw bulls` mx, as distinguished from rthe bottoms wax'y employed inthe preceeding examples, a u black Mid-Continent soft b ulk wax, i'rom which.y lhardviraxescould not vbe obtained by ordinary, 'methods unless the yields were kept very llowy by employing, usually high illtration temperatures, wasv treated with 15%- by weight of 93% sulfuric acid inthe presence oft-% liquid propane at -145`F.^, and desludged 'by settling. One'porf tion was chilled'` and illtered without the addition i .of .'clay,' and the'resultlng wax fractions contacted vwith 10% clayand another` portion was similarly illtered, but in the presenceof 2% nely divided ,clayl the clay beingv addedbeiorev each chilling.

step, andthe wax fractions rwere recovered to ccntact thewaxl with the clay contained therein,v without thefurther additionr of clay.v The re-N ysuits are shown in' 'I able IV: y,

.'Ifoshow that the clay improves the fractio'na#rk tion' emcien'cyeven in the case where the wax has not been acid'treat'edraw bulk wax' described f ln Example IV,Awasheated in the presence of 5% ,asphalty and 600%'by volume of liquidzpropan'e tor 155=160 F., and the asphalt layer removed.y One portion was chilled andfiltered in the absence of clay, andthe resulting wax fractions contacted rwith10'% ofcly; and anotherportion was chilled andflltere'd in the presence of 2% nely .dividedr clay, addedbefore veachstepof' chilling, and the i resulting wax vfractions were warmed to contact' 3 the w'ox with the oiey; without the nirtner oddition i' clay. The results are shown in PTable V.:

Table V Peroeut ils-TM Elem@ by wei ht NPA ooior melting 82M YM point tion t 'Y "F.

Original sample 100 Black 132 Wax ltcrtid without 7.5. N.T.(o 1.o s 135 5.6 8+ 125 cla no 10.0 Ds+ 2o 14s"y r 10.5 N. T. (o) 14o 1 5.o 4+ 144 24 (a) Not transparent. v

A comparison of the results obtained in Exam-l ples IV and V shows the marked improvement yin iractionation'eillciency, and a marked improvement in'theyield and melting point oi.' hard waxes dueto preliminary acid treatment, and fractional precipitation vfrom the acid medium. Moreover, the results in Table V show that the precipitation inthe presence o1V iinely divided 'clay is useful although the wax hasv not been acid treated. f

Referring to the drawing representinga flow diagram 'ot asemi-continuous version of our process: Wax is melted in tank I by steam in coil 2. The molten wax is diluted in line 3 with a suitable ksolvent from line l and the resulting wax solution having a temperature suilicientlyv high to prevent precipitation of wax is mixed with acid from line 5 in mixerv l. The mixture so obtained enters settling tank I where acidsludge is settled out and is withdrawn 'through line `8. The supernatant acid-reacting wax solution, substantially free from sludge but having an acidity above 0.2 milli-A grams KOH per ygram lof solution, may now be withdrawn through line 9 and mixed with clay whiohis introduced through une In either in the form of a dryA powder or as a slurry rin asuitable carrier liquid suchy as low-boiling hydrocarbon liquid. If desired, the addition of clay can be omitted. The solution which preferablycontains clay isnow chilled in chiller II to a predetermined desired' low temperature. Wax which precipitates,

together with suspended clay, if clay is present,l is retained in filter I2, which filter isadvantageously of Aa continuous type.v 'The filtrate proceeds to one of the tanks I3 or I4, to be recirculated' when the supply of the original wax from tank 'I `is shut ofi, through line I5, chiller II, filter I2,

into the other of the two tanks I3 or'Il.` The chilling temperature is lower than therst'time and a fresh amount of clay is advantageously added to the reclrculating solution. The recirr culation may be repeated a. number of times at consecutively lower `temperatures until substantially'all o! the wax inthe solution has been fractionally precipitated and filtered out;

The iinal illtrate is discarded through line I6.-

Theseveral batches of wax from illter I2 are introduced lnto'contactor Il through line I8. If

the lwax contains no clay, clay may be added through line I9. Heat for the contacting is provided in any conventional manner as by means of a heating coil 20. Solvent vapors escape through line 2| while the contacted wax is withdrawn through line 22 to be ltered in illter 23. Wax,

free from clay, goes through line 24 to the wax molds, and spent clay is discarded through line 2B. We claim as our invention: 1. The process for producing light colored, high melting wax from dark colored, normally solid:

solution, chilling the sour substantially sludgefree wax-diluent solution to solidify only a portion ofy the wax, and separating the solidified wax from the liquid wax-diluent solution without additional acid. l

2. The process for producing light colored, highmelting wax from dark colored, normally solid paraflin wax of lower melting point which comprises contacting the wax in the liquid state with concentrated sulfuricA acid at an elevated temperature of the order of 140 F. in the presence of a low-boiling paraillnic diluent which is substantially resistant to the action oil strong sulfuric acid under the conditions of the treatment, removing the resulting sludge from the wax-diluent solution, chilling the sour substantially sludge-free wax-diluent solution to solidify only a portion of the wax, and separating the solidified wax from the liquid wax-diluent solution without additional acid.

3. 'I'he process for producing light colored, high melting wax from dark colored, normally' solid parailln wax of lower melting point, which comprises contacting the wax in the liquid state with concentrated sulfuric acid -at an elevated temperature of the order of 140 F., in the presence of a thinning diluent capable of dissolving said dark-colored parailln wax and substantially resistant to the action yof concentrated sulfuric acid under the conditions of the treatment, removing the resulting sludge from the wax-diluent solution, chilling the sour substantially `sludge-- free wax-diluent solution to solidify only a portion of the wax, and separating the solidified wax from the liquid wax-diluent solution without additional acid.

4. The process for producing light colored, high melting wax from dark colored, normally solid paraiiln wax of lower melting point,` which comprises contacting the wax in the vliquid state with concentrated sulfuric acidat an elevated temperature of the order of 140 F., in the presence of a thinning diluent capable of dissolving said dark-colored parailin wax and substantially resistant tothe action of concentrated sulfuric acid under the conditions ofthe treatment, removing the resulting sludge from the Wax-diluent solution, chilling the sour substantially sludgefree wax-diluent solution to solidify only a portion of the wax. separating the solidified wax from the liquid wax-diluent solution without additional acid, and contacting the separated solidied wax in the liquid state with clay.

5. 'Ihe process for producing light colored, high melting wax from dark colored, normally solid paraiiln wax of lower melting point which comprises contacting the wax in the liquid state with concentrated sulfuric acid at an elevated temperature of the order of 140 F., in the presence of a low-boiling hydrocarbon diluent which is substantially resistant to the action of strong alcun sulfuric acid under the conditionsof the treatment. removing the resulting sludge. from the wax-diluent solution, adding a small quantity of a pulverized granular material to thesour substantially sludge-free solution, chilling the re- 5 sulting mixture while maintaining the granular material in suspension, to solidify only a portion of the wax, and separating the solidiiiedwax from the liquid wax-diluent solution without additional acid.

6; The process for producing light colored, high melting wax from dark colored, normally solid paraflln wax of lower melting point which comprises contacting the wax in the liquid state with concentrated sulfuric acid at an elevated temperature of the order of 140 F., in thev presence of a low-boiling hydrocarbon diluent which is substantially resistant to the action of strong sulfuric acid under the conditions of the treatment, removing the resulting sludge from the wax-diluent solution, adding a small quantityof pulverized clay to the sour substantially sludge-free solution, chilling the resulting mixture while maintaining the pulverized clay in suspension, to solidify only a portion of the wax, separating the solidified wax from the liquid wax-diluent solution without additional acid, warming the separated solidiiled wax to melt it, and removing the clay from the molten wax by mechanical means.

'7. The process for' producing. light-colored 3o high-melting wax from dark-colored, normally solid paramn wax of lower melting point, which comprises contacting the wax in the liquid state with concentrated sulfuric acid,- at a temperature of the order of 140 F. in the presence of a `thinning diluent capable of dissolving said dark-colored parailln wax and being substantially resistant to the action of the concentrated sulfuric acid under the conditions of the treatment, removing the resulting sludge from the waxm diluent solution under conditions to produce a sour substantially sludge-free oil having an acidity above .2 milligram KOH per gram of solution, chilling the sour wax-diluent solution to solidifyy only a portion of the wax, yand separating the solidied wax from the liquid wax-diluent solution without additional acid.

8.In the process of producing light-colored, high-melting wax from dark-colored, normally solid paraiiin wax of lower melting point, which comprises contacting the wax in the liquid state with concentrated sulfuric acid at a temperature of the order of 140 F. in the presence of a low-boling hydrocarbon diluent whichis substantially resistant to the action of concentrated sulfuric acid under the conditions of the treatment, removing the resulting sludge from the wax-diluent solution, adding between .5 to 5% of pulverized clay to the sour substantially sludge-free solution, chilling the resulting mix.- ture while maintaining the pulverized clay in suspension to solidify only a portion of the wax, and separating the solidied wax from the liquid wax-diluent solution without additional acid.

9. The process of producing light-colored, high-melting wax from dark-colored, normally solid paramn Wax of lower melting point, which comprises contacting one volume of the wax in the liquid state in the presence of 1 to 8 volumes of a thinning diluent capable of dissolving said l dark-colored paraiiln wax and being substantially resistant to the action of concentrated sulfurie acid under the conditions of the treatment, treating the resulting solution with concentrated sulfuric acid at a temperature o f the order of 140 F.. removing the resulting sludge from the wax-diluent solution, chilling the sour substantially sludge-free wax-diluent solution to solidify only a portion of the wax and separating the solidined wax from the liquid wax-diluent solution without additional acid.

10. In the process of fractionating dark-colored paraln wax of low-melting p'oint to produce fractions of lighter colored `wax having higher melting points, the steps comprising dissolving the dark-colored wax in a low boiling vhydrocarbon solvent which is substantially resistant to the action of concentrated sulfuric acid under the conditions o1' the treatment, treating the resulting solution with sulfuric acid at a temperature of the order of 140 F. to produce a sludge, removing the sludge under conditions to produce a sour substantially sludge-free oil having an acidity above .2 milligram KOH per gram of solution, chilling said sour oil to effect precipitation only of a portion of the wax, separating said precipitated portion without additional acid and further chilling the remaining another portion of the wax.

ALVIN P. ANDERSON. EDWARD J. JAHN. 

